Nitrile rubber glove based on material self-repairing and preparation process

Abstract

This invention belongs to the field of polymer materials technology, specifically relating to a nitrile rubber glove based on material self-healing and its preparation process. The raw materials of the nitrile rubber glove include the following components by weight: 50-70 parts modified nitrile latex, 10-15 parts silane-modified nano silica, 0.5-1 part vulcanizing agent, 0.25-0.35 parts accelerator, 0.5-1 part crosslinking agent, 7-12 parts coordination salt, 4-6 parts 1,4-butanediol di(3-mercaptopropionate), 1-3 parts antioxidant, and 55-65 parts deionized water. The nitrile rubber gloves prepared by this invention have good mechanical properties, including a tensile strength of 32-35 MPa, a puncture resistance grade of 4, an abrasion resistance grade of 4, a tear resistance grade of 4, and a cut resistance grade of 3. They also have good self-healing ability, and can quickly self-repair minor damage within 5 minutes at room temperature, and can quickly self-repair puncture or tear damage after being heated to above 60°C for about 20-30 minutes.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a nitrile rubber glove based on material self-healing and its preparation process. Background Technology

[0002] Nitrile rubber (NBR) is widely used in gloves for medical protection, industrial operations, and laboratories due to its excellent oil resistance, chemical corrosion resistance, aging resistance, and good mechanical strength. However, NBR is a cross-linked thermosetting material with a three-dimensional network structure formed by traditional vulcanization processes. This network structure lacks reversibility, restricting the free movement of molecular chains and thus limiting its self-healing properties.

[0003] Traditional nitrile rubber gloves are easily punctured or torn by sharp objects (such as needles or metal fragments) during use, and cannot repair themselves after being damaged, resulting in a sharp drop in the protective performance of the gloves. They need to be replaced in time, which not only increases the cost of use, but may also lead to safety accidents (such as medical staff coming into contact with patients' blood or industrial operations coming into contact with corrosive liquids) if the damage is not detected in time.

[0004] In recent years, self-healing materials have become a research hotspot in the field of polymer materials because they can repair damage by responding to external stimuli (such as temperature, light, pH, etc.) through their own structure. Among them, shape memory polymers (SMPs) have shown unique advantages in the field of self-healing due to their intelligent properties of "fixing temporary shape - triggering shape recovery": when a material develops cracks or holes due to external forces, SMPs can restore their original structure through molecular chain segment movement under specific conditions (such as body temperature, specific wavelength light), thereby closing the damaged area; or microcapsule repair agents can be dispersed in acrylonitrile rubber matrix, and when damaged, the microcapsules rupture to release the repair agent, thereby achieving the repair of the acrylonitrile rubber.

[0005] However, the following defects also occurred when functional components SMP and microcapsule repair agents were added, such as: low number of repair cycles; poor dispersion uniformity of microcapsule repair agents in nitrile rubber, resulting in localized reduction of nitrile rubber strength or uneven repair ability, and low self-repair efficiency after multiple damages; the addition of functional component SMP will affect the puncture resistance of nitrile rubber.

[0006] Therefore, developing a self-healing nitrile rubber glove to solve the problem of the unrepairability of traditional nitrile gloves and improve the mechanical properties of nitrile rubber gloves has significant practical value and market prospects. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides a nitrile rubber glove based on material self-healing and its preparation process. The raw materials of the nitrile rubber glove include the following components by weight: 50-70 parts modified nitrile latex, 10-15 parts silane-modified nano silica, 0.5-1 part vulcanizing agent, 0.25-0.35 parts accelerator, 0.5-1 part crosslinking agent, 7-12 parts coordination salt, 4-6 parts 1,4-butanediol di(3-mercaptopropionate), 1-3 parts antioxidant, and 55-65 parts deionized water.

[0008] The manufacturing process of the nitrile rubber gloves based on material self-healing includes the following steps:

[0009] S11. Silane-modified nano-silica is stirred and mixed with 1,4-butanediol di(3-mercaptopropionate) to uniformly coat the surface of the silane-modified nano-silica, yielding component A; the coordination salt, vulcanizing agent, accelerator, and crosslinking agent are added to deionized water and stirred for 20-30 minutes to obtain component B; component A and antioxidant are added to modified nitrile latex, and the mixture is heated to 40-50℃ and stirred for 20-30 minutes to obtain component C;

[0010] S12. Add component B to component C and stir to obtain composite nitrile rubber latex; immerse the glove blank preheated to 50-60℃ in a calcium chloride aqueous solution with a mass fraction of 2-4wt% for 3-5 seconds, then immerse it in the composite nitrile rubber latex for 4-8 seconds, vulcanize and dry at 70-80℃ for 30-40 minutes, then raise the temperature to 120-130℃ and continue vulcanizing and drying for 50-60 minutes to obtain nitrile rubber gloves.

[0011] Preferably, the preparation method of the modified nitrile latex includes the following steps:

[0012] S21: Add acrylonitrile, cinnamic acid, emulsifier, and dodecyl mercaptan to deionized water, stir for 15-20 minutes to emulsify, then add to a reaction vessel, purge with nitrogen to remove oxygen, then add butadiene and ammonium persulfate to obtain a mixed emulsion, stir at 5-10℃ until the conversion rate is 60-70%;

[0013] S22. Add emulsifier and dodecyl mercaptan to the system and stir the reaction until the conversion rate is above 98%;

[0014] S23. Add sodium sulfite aqueous solution as a terminator to the system, degas under vacuum to remove unreacted monomers and impurities, filter, and adjust the pH to 8-9 to obtain modified nitrile latex.

[0015] Preferably, the raw materials for preparing the modified nitrile latex are as follows by weight: 25-35 parts acrylonitrile, 3-5 parts cinnamic acid, 50-70 parts butadiene, 1-2 parts emulsifier, 0.05-0.2 parts dodecyl mercaptan, 0.1-0.2 parts ammonium persulfate, 5-7 parts sodium sulfite aqueous solution, and 500-600 parts deionized water.

[0016] Preferably, the emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium stearate.

[0017] Preferably, the sodium sulfite aqueous solution has a mass fraction of 10-15%.

[0018] Preferably, the amount of emulsifier added in S21 is 60-70% of the total amount of emulsifier, and the amount of emulsifier added in S22 is 30-40% of the total amount of emulsifier.

[0019] Preferably, the amount of dodecyl mercaptan added in S21 is 70-80% of the total amount of dodecyl mercaptan, and the amount of dodecyl mercaptan added in S22 is 20-30% of the total amount of dodecyl mercaptan.

[0020] Preferably, the method for preparing the silane-modified nano-silica is as follows:

[0021] KH550 was added to an ethanol solution, the pH was adjusted to 3-5, and the mixture was stirred at room temperature for 15-30 min. Then, nano-silica was added and ultrasonically dispersed for 10-20 min. The mixture was stirred at room temperature for 3-4 h. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and vacuum dried to obtain silane-modified nano-silica.

[0022] Furthermore, the particle size of the nano-silica is 50-100 nm; the mass ratio of KH550 to nano-silica is 1:15-20.

[0023] Furthermore, the mass ratio of KH550 to ethanol solution is 1:20-30; the mass fraction of ethanol solution is 90%-95%.

[0024] Preferably, the vulcanizing agent is one of sulfur, zinc oxide, and dicumyl peroxide.

[0025] Preferably, the accelerator is one or more of TMTD and DM.

[0026] Preferably, the crosslinking agent is a polyol crosslinking agent such as glyceryl acrylate, trimethylolpropane, or polyethylene glycol.

[0027] Preferably, the coordination salt is one or more of zinc sulfate, copper sulfate, ferric sulfate, zinc chloride, copper chloride, and ferric chloride.

[0028] Preferably, the antioxidant is 2,6-di-tert-butyl-p-cresol or N-isopropyl-N'-phenyl-p-phenylenediamine.

[0029] Cinnamic acid contains carboxyl and aromatic groups; therefore, the modified nitrile rubber latex obtained by ternary copolymerization of butadiene, acrylonitrile, and cinnamic acid contains cyano, carboxyl, and aromatic groups. Under the action of vulcanizing agents and accelerators, nitrile rubber molecules crosslink through covalent bonds; the crosslinking agent reacts with the carboxyl groups in the modified nitrile rubber latex to further crosslink through non-covalent bonds. Simultaneously, the cyano and aromatic groups in the modified nitrile rubber latex coordinate with coordinating salts to obtain a dual dynamic reversible crosslinking structure. The two form a network system combining covalent and non-covalent bonds, achieving its self-healing properties.

[0030] The aromatic groups in the modified nitrile rubber latex obtained by ternary copolymerization of butadiene, acrylonitrile, and cinnamic acid have a rigid structure. Although this improves the mechanical properties and abrasion resistance of nitrile rubber gloves to some extent, they harden or even become brittle at low temperatures, failing to fit the hand well. Therefore, the filler was treated by uniformly coating the surface of silane-modified nano-silica with 1,4-butanediol di(3-mercaptopropionate). This not only improves the dispersibility of nano-silica, but also, because 1,4-butanediol di(3-mercaptopropionate) contains a flexible structure, the thiol groups in 1,4-butanediol di(3-mercaptopropionate) generate disulfide bonds for crosslinking under the high-temperature oxidation environment in step S12. This not only toughens the material and prevents low-temperature embrittlement, but also enhances the puncture resistance of the material due to the increased crosslinking density. The overall structure of the material is more stable, and the synergistic effect of dynamic reversible crosslinking structures such as disulfide bonds and coordination bonds further improves the self-healing properties of the material.

[0031] The beneficial effects of this invention are as follows:

[0032] 1. The nitrile rubber gloves prepared by this invention have good mechanical properties, including a tensile strength of 32-35 MPa, a puncture resistance grade of 4, an abrasion resistance grade of 4, a tear resistance grade of 4, and a cut resistance grade of 3.

[0033] 2. The nitrile rubber gloves prepared by this invention have good self-healing ability. They can quickly self-heal within 5 minutes at room temperature for minor damage, and can quickly self-heal after being heated to above 60°C for about 20 to 30 minutes for puncture or tear damage.

[0034] 3. The nitrile rubber gloves prepared by this invention are suitable for low-temperature environments and have a low embrittlement temperature.

[0035] 4. This invention does not require the addition of plasticizers during the preparation process. The multiple cross-linking structure can meet the performance requirements of nitrile rubber gloves such as flexibility and abrasion resistance. Not only is the performance more stable, but it can also avoid potential safety hazards to the human body caused by plasticizer residues or precipitation. Detailed Implementation

[0036] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0037] Example 1: A self-healing nitrile rubber glove and its preparation process. The raw materials of the nitrile rubber glove include the following components by weight: 60 parts modified nitrile latex, 12 parts silane-modified nano silica, 0.7 parts vulcanizing agent, 0.3 parts accelerator, 0.8 parts crosslinking agent, 10 parts coordination salt, 5 parts 1,4-butanediol di(3-mercaptopropionate), 2 parts antioxidant, and 60 parts deionized water.

[0038] The manufacturing process of the nitrile rubber gloves based on material self-healing includes the following steps:

[0039] S11. Silane-modified nano-silica is stirred and mixed with 1,4-butanediol di(3-mercaptopropionate) to uniformly coat the surface of the silane-modified nano-silica, yielding component A; the coordination salt, vulcanizing agent, accelerator, and crosslinking agent are added to deionized water and stirred for 25 minutes to obtain component B; component A and antioxidant are added to modified nitrile latex, heated to 45℃ and stirred for 30 minutes to obtain component C;

[0040] S12. Add component B to component C and stir to obtain composite nitrile rubber latex; immerse the glove blank preheated to 55°C in a 3wt% calcium chloride aqueous solution for 4 seconds, then immerse it in the composite nitrile rubber latex for 6 seconds, vulcanize and dry at 75°C for 40 minutes, then raise the temperature to 125°C and continue vulcanizing and drying for 55 minutes to obtain nitrile rubber gloves.

[0041] The preparation method of the modified nitrile rubber latex includes the following steps:

[0042] S21: Acrylonitrile, cinnamic acid, emulsifier, and dodecyl mercaptan are added to deionized water and stirred for 20 minutes to emulsify. The mixture is then added to a reaction vessel, and nitrogen gas is purged to remove oxygen. Butadiene and ammonium persulfate are then added to obtain a mixed emulsion. The mixture is stirred at 7°C until the conversion rate reaches 65%.

[0043] S22. Add emulsifier and dodecyl mercaptan to the system and stir the reaction until the conversion rate is 99%;

[0044] S23. Add sodium sulfite aqueous solution as a terminator to the system, degas under vacuum to remove unreacted monomers and impurities, filter, and adjust the pH to 8.5 to obtain modified nitrile latex.

[0045] The raw materials for preparing the modified nitrile latex are as follows by weight: 30 parts acrylonitrile, 4 parts cinnamic acid, 60 parts butadiene, 1.5 parts emulsifier, 0.15 parts dodecyl mercaptan, 0.15 parts ammonium persulfate, 6 parts sodium sulfite aqueous solution, and 550 parts deionized water.

[0046] The emulsifier is sodium dodecylbenzenesulfonate.

[0047] The sodium sulfite aqueous solution has a mass fraction of 13%.

[0048] In S21, the amount of emulsifier added is 65% of the total amount of emulsifier, and in S22, the amount of emulsifier added is 35% of the total amount of emulsifier.

[0049] The amount of dodecyl mercaptan added in S21 is 75% of the total amount of dodecyl mercaptan, and the amount of dodecyl mercaptan added in S22 is 25% of the total amount of dodecyl mercaptan.

[0050] The preparation method of the silane-modified nano-silica is as follows:

[0051] KH550 was added to an ethanol solution, the pH was adjusted to 4, and the mixture was stirred at room temperature for 20 min. Then, nano-silica was added and ultrasonically dispersed for 15 min. The mixture was stirred at room temperature for 3.5 h. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and vacuum dried to obtain silane-modified nano-silica.

[0052] The particle size of the nano-silica is 80 nm; the mass ratio of KH550 to nano-silica is 1:17.

[0053] The mass ratio of KH550 to ethanol solution is 1:25; the mass fraction of ethanol solution is 93%.

[0054] The vulcanizing agent is dicumyl peroxide, and the accelerator is TMTD.

[0055] The crosslinking agent is glyceryl acrylate; the coordinating salt is zinc sulfate; and the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0056] Example 2: A self-healing nitrile rubber glove and its preparation process. The raw materials of the nitrile rubber glove include the following components by weight: 50 parts modified nitrile latex, 10 parts silane-modified nano silica, 0.5 parts vulcanizing agent, 0.25 parts accelerator, 0.5 parts crosslinking agent, 7 parts coordination salt, 4 parts 1,4-butanediol di(3-mercaptopropionate), 1 part antioxidant, and 55 parts deionized water.

[0057] The manufacturing process of the nitrile rubber gloves based on material self-healing includes the following steps:

[0058] S11. Silane-modified nano-silica is stirred and mixed with 1,4-butanediol di(3-mercaptopropionate) to uniformly coat the surface of the silane-modified nano-silica, yielding component A; coordination salt, vulcanizing agent, accelerator, and crosslinking agent are added to deionized water and stirred for 20 minutes to obtain component B; component A and antioxidant are added to modified nitrile latex, heated to 40℃ and stirred for 20 minutes to obtain component C;

[0059] S12. Add component B to component C and stir to obtain composite nitrile rubber latex; immerse the glove blank preheated to 50°C in a 2wt% calcium chloride aqueous solution for 3 seconds, then immerse it in the composite nitrile rubber latex for 4 seconds, vulcanize and dry at 70°C for 30 minutes, then raise the temperature to 120°C and continue vulcanizing and drying for 50 minutes to obtain nitrile rubber gloves.

[0060] The preparation method of the modified nitrile rubber latex includes the following steps:

[0061] S21: Acrylonitrile, cinnamic acid, emulsifier, and dodecyl mercaptan are added to deionized water and stirred for 15 minutes to emulsify. The mixture is then added to a reaction vessel, and nitrogen gas is purged to remove oxygen. Butadiene and ammonium persulfate are then added to obtain a mixed emulsion. The mixture is stirred at 5°C until the conversion rate reaches 60%.

[0062] S22. Add emulsifier and dodecyl mercaptan to the system and stir the reaction until the conversion rate reaches 98%;

[0063] S23. Add sodium sulfite aqueous solution as a terminator to the system, degas under vacuum to remove unreacted monomers and impurities, filter, and adjust the pH to 8 to obtain modified nitrile latex.

[0064] The raw materials for preparing the modified nitrile latex are as follows by weight: 25 parts acrylonitrile, 3 parts cinnamic acid, 50 parts butadiene, 1 part emulsifier, 0.05 parts dodecyl mercaptan, 0.1 parts ammonium persulfate, 5 parts sodium sulfite aqueous solution, and 500 parts deionized water.

[0065] The emulsifier is sodium dodecylbenzenesulfonate.

[0066] The sodium sulfite aqueous solution has a mass fraction of 15%.

[0067] In S21, the amount of emulsifier added is 60% of the total amount of emulsifier, and in S22, the amount of emulsifier added is 40% of the total amount of emulsifier.

[0068] The amount of dodecyl mercaptan added in S21 is 70% of the total amount of dodecyl mercaptan, and the amount of dodecyl mercaptan added in S22 is 30% of the total amount of dodecyl mercaptan.

[0069] The preparation method of the silane-modified nano-silica is as follows:

[0070] KH550 was added to an ethanol solution, the pH was adjusted to 3, and the mixture was stirred at room temperature for 15 min. Then, nano-silica was added and ultrasonically dispersed for 10 min. The mixture was stirred at room temperature for 3 h. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and vacuum dried to obtain silane-modified nano-silica.

[0071] The particle size of the nano-silica is 50 nm; the mass ratio of KH550 to nano-silica is 1:15.

[0072] The mass ratio of KH550 to ethanol solution is 1:20; the mass fraction of ethanol solution is 90%.

[0073] The vulcanizing agent is dicumyl peroxide; the accelerator is TMTD.

[0074] The crosslinking agent is trimethylolpropane, the coordination salt is copper sulfate, and the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0075] Example 3: A self-healing nitrile rubber glove and its preparation process. The raw materials of the nitrile rubber glove include the following components by weight: 70 parts modified nitrile latex, 15 parts silane-modified nano silica, 1 part vulcanizing agent, 0.35 parts accelerator, 1 part crosslinking agent, 12 parts coordination salt, 6 parts 1,4-butanediol di(3-mercaptopropionate), 3 parts antioxidant, and 65 parts deionized water.

[0076] The manufacturing process of the nitrile rubber gloves based on material self-healing includes the following steps:

[0077] S11. Silane-modified nano-silica is stirred and mixed with 1,4-butanediol di(3-mercaptopropionate) to uniformly coat the surface of the silane-modified nano-silica, yielding component A; coordination salt, vulcanizing agent, accelerator, and crosslinking agent are added to deionized water and stirred for 30 min to obtain component B; component A and antioxidant are added to modified nitrile latex, heated to 50℃ and stirred for 25 min to obtain component C;

[0078] S12. Add component B to component C and stir to obtain composite nitrile rubber latex; immerse the glove blank preheated to 60°C in a 4wt% calcium chloride aqueous solution for 5 seconds, then immerse it in the composite nitrile rubber latex for 8 seconds, vulcanize and dry at 80°C for 40 minutes, then raise the temperature to 130°C and continue vulcanizing and drying for 60 minutes to obtain nitrile rubber gloves.

[0079] The preparation method of the modified nitrile rubber latex includes the following steps:

[0080] S21: Acrylonitrile, cinnamic acid, emulsifier, and dodecyl mercaptan are added to deionized water and stirred for 20 minutes to emulsify. The mixture is then added to a reaction vessel, and nitrogen gas is purged to remove oxygen. Butadiene and ammonium persulfate are then added to obtain a mixed emulsion. The mixture is stirred at 10°C until the conversion rate reaches 70%.

[0081] S22. Add emulsifier and dodecyl mercaptan to the system and stir the reaction until the conversion rate is 99%;

[0082] S23. Add sodium sulfite aqueous solution as a terminator to the system, degas under vacuum to remove unreacted monomers and impurities, filter, and adjust the pH to 9 to obtain modified nitrile latex.

[0083] The raw materials for preparing the modified nitrile latex are as follows by weight: 35 parts acrylonitrile, 5 parts cinnamic acid, 70 parts butadiene, 2 parts emulsifier, 0.2 parts dodecyl mercaptan, 0.2 parts ammonium persulfate, 7 parts sodium sulfite aqueous solution, and 600 parts deionized water.

[0084] The emulsifier is sodium dodecylbenzenesulfonate.

[0085] The sodium sulfite aqueous solution has a mass fraction of 10%.

[0086] In S21, the amount of emulsifier added is 70% of the total amount of emulsifier, and in S22, the amount of emulsifier added is 30% of the total amount of emulsifier.

[0087] The amount of dodecyl mercaptan added in S21 is 80% of the total amount of dodecyl mercaptan, and the amount of dodecyl mercaptan added in S22 is 20% of the total amount of dodecyl mercaptan.

[0088] The preparation method of the silane-modified nano-silica is as follows:

[0089] KH550 was added to an ethanol solution, the pH was adjusted to 5, and the mixture was stirred at room temperature for 30 min. Then, nano-silica was added and ultrasonically dispersed for 20 min. The mixture was stirred at room temperature for 4 h. After the reaction was completed, the nano-silica was obtained by centrifugation, washing with anhydrous ethanol, and vacuum drying.

[0090] The particle size of the nano-silica is 100 nm; the mass ratio of KH550 to nano-silica is 1:20.

[0091] The mass ratio of KH550 to ethanol solution is 1:30; the mass fraction of ethanol solution is 95%.

[0092] The vulcanizing agent is dicumyl peroxide, and the accelerator is TMTD.

[0093] The crosslinking agent is glyceryl acrylate, and the coordination salt is zinc sulfate.

[0094] The antioxidant is 2,6-di-tert-butyl-p-cresol.

[0095] Comparative Example 1: A representative example, Example 1, was selected. 1,4-Butanediol di(3-mercaptopropionate) was removed from the nitrile rubber glove raw material. All other components were the same as in Example 1. This was used as Comparative Example 1.

[0096] Comparative Example 2: A representative example, Example 1, was selected, in which cinnamic acid in the raw material for preparing modified nitrile latex was replaced with acrylic acid, while the rest remained the same as in Example 1. This was used as Comparative Example 2.

[0097] The nitrile rubber gloves prepared in Examples 1-3 and Comparative Examples 1-2 were tested according to EN388 standard, and the specific results are shown in Table 1.

[0098] Testing items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Commercially available nitrile rubber gloves Tensile strength (MPa) 35 32 34 24.5 28 19 Puncture resistance level 4 4 4 3 3 1 Abrasion resistance rating 4 4 4 4 3 3 Tear resistance rating 4 4 4 3 3 2 Cut resistance rating 3 3 3 3 2 1

[0099] The self-healing properties of the nitrile rubber gloves prepared in Examples 1-3 and Comparative Examples 1-2 were tested, as detailed in Table 2.

[0100] Table 2

[0101] Testing items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Self-repair efficiency (%) 88 86 87 80 84 Self-repair efficiency after 5 cycles (%) 80 75 78 67 75

[0102] The testing method is as follows: The nitrile rubber gloves prepared in Examples 1-3 and Comparative Examples 1-2 were made into dumbbell-shaped samples (50×4 mm in length and width). They were broken at a rate of 50 mm / min using an electronic universal testing machine. The samples were then placed at 70°C for 30 min to self-repair, and their self-repair efficiency was tested. This was repeated 5 times to test their self-repair efficiency.

[0103] The embrittlement temperature of the nitrile rubber gloves prepared in Examples 1-3 and Comparative Examples 1-2 was tested according to ASTM D746, as shown in Table 3.

[0104] Table 3

[0105] Testing items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Embrittlement temperature (°C) -52 -50 -51 -38 -55

[0106] Unless otherwise specified, all proportions and percentages mentioned in this invention are mass proportions and mass percentages; all raw materials are commercially available.

[0107] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A material self-repairing based nitrile rubber glove, characterized in that, The raw materials for the nitrile rubber gloves include the following components by weight: 50-70 parts modified nitrile latex, 10-15 parts silane-modified nano silica, 0.5-1 part vulcanizing agent, 0.25-0.35 parts accelerator, 0.5-1 part crosslinking agent, 7-12 parts coordination salt, 4-6 parts 1,4-butanediol di(3-mercaptopropionate), 1-3 parts antioxidant, and 55-65 parts deionized water; The manufacturing process of the nitrile rubber gloves based on material self-healing includes the following steps: S11. Silane-modified nano-silica is stirred and mixed with 1,4-butanediol di(3-mercaptopropionate) to uniformly coat the surface of the silane-modified nano-silica, yielding component A; coordination salt, vulcanizing agent, accelerator, and crosslinking agent are added to deionized water and stirred for 20-30 minutes to obtain component B; component A and antioxidant are added to modified nitrile latex, and the mixture is heated to 40-50℃ and stirred for 20-30 minutes to obtain component C; S12. Add component B to component C and stir to obtain composite nitrile rubber latex; immerse the glove blank preheated to 50-60℃ in a calcium chloride aqueous solution with a mass fraction of 2-4wt% for 3-5 seconds, then immerse it in the composite nitrile rubber latex for 4-8 seconds, vulcanize and dry at 70-80℃ for 30-40 minutes, then raise the temperature to 120-130℃ and continue vulcanizing and drying for 50-60 minutes to obtain nitrile rubber gloves; The raw materials for preparing the modified nitrile latex are as follows by weight: 25-35 parts acrylonitrile, 3-5 parts cinnamic acid, 50-70 parts butadiene, 1-2 parts emulsifier, 0.05-0.2 parts dodecyl mercaptan, 0.1-0.2 parts ammonium persulfate, 5-7 parts sodium sulfite aqueous solution, and 500-600 parts deionized water.

2. The nitrile rubber glove based on material self-healing according to claim 1, characterized in that, The preparation method of the modified nitrile rubber latex includes the following steps: S21: Add acrylonitrile, cinnamic acid, emulsifier, and dodecyl mercaptan to deionized water, stir for 15-20 minutes to emulsify, then add to a reaction vessel, purge with nitrogen to remove oxygen, then add butadiene and ammonium persulfate to obtain a mixed emulsion, stir at 5-10℃ until the conversion rate is 60-70%; S22. Add emulsifier and dodecyl mercaptan to the system and stir the reaction until the conversion rate is above 98%; S23. Add sodium sulfite aqueous solution as a terminator to the system, degas under vacuum to remove unreacted monomers and impurities, filter, and adjust the pH to 8-9 to obtain modified nitrile latex.

3. A material self-repairing based nitrile rubber glove according to claim 1, characterized in that, The emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium stearate; The sodium sulfite aqueous solution has a mass fraction of 10-15%.

4. A material self-repairing based nitrile rubber glove according to claim 2, characterized in that, The amount of emulsifier added in S21 is 60-70% of the total amount of emulsifier, and the amount of emulsifier added in S22 is 30-40% of the total amount of emulsifier; The amount of dodecyl mercaptan added in S21 is 70-80% of the total amount of dodecyl mercaptan, and the amount of dodecyl mercaptan added in S22 is 20-30% of the total amount of dodecyl mercaptan.

5. A nitrile rubber glove based on material self-healing according to claim 1, characterized in that, The preparation method of the silane-modified nano-silica is as follows: KH550 was added to an ethanol solution, the pH was adjusted to 3-5, and the mixture was stirred at room temperature for 15-30 min. Then, nano-silica was added and ultrasonically dispersed for 10-20 min. The mixture was stirred at room temperature for 3-4 h. After the reaction was completed, the mixture was centrifuged, washed with anhydrous ethanol, and vacuum dried to obtain silane-modified nano-silica.

6. A nitrile rubber glove based on material self-healing according to claim 5, characterized in that, The particle size of the nano-silica is 50-100 nm; the mass ratio of KH550 to nano-silica is 1:15-20; The mass ratio of KH550 to ethanol solution is 1:20-30; the mass fraction of ethanol solution is 90%-95%.

7. A nitrile rubber glove based on material self-healing according to claim 1, characterized in that, The vulcanizing agent is one of sulfur, zinc oxide, and dicumyl peroxide; The accelerator is one or more of TMTD and DM; The crosslinking agent is one of glyceryl acrylate, trimethylolpropane, and polyethylene glycol.

8. A nitrile rubber glove based on material self-healing according to claim 1, characterized in that, The coordination salt is one or more of zinc sulfate, copper sulfate, ferric sulfate, zinc chloride, copper chloride, and ferric chloride. The antioxidant is 2,6-di-tert-butyl-p-cresol or N-isopropyl-N'-phenyl-p-phenylenediamine.